P-phenylenediamine developer containing nu-alkylacetamido ethyl substituent



Patented Apr. 8, 1952 2,592,363 P-PHENYLENEDIAMNE DEVELOPER ooN- TAININGN-ALKYLACETAMIDO SUBSTITUENT ETHYL Arnold Weissberger, Dudley B. Glass,and Paul W. Vittum, Rochester, N. Y., assignors to Eastman KodakCompany, Rochester, N. Y., a corporation of New Jersey No Drawing.Application March 6, 1948, Serial No. 13,525

4 Claims.

This invention relates to photographic developers and more particularlyto photographic developers containing an N-alkyl acetamido ethylsubstituent.

It is known that photographic developers of the pphenylenediamine typeare valuable compounds for producing fine grain black and whitephotographic images and also that these compounds, especially when theycontain alkyl substituents on one of the nitrogen atoms, are useful asdevelopers in producing colored photographic images. A seriousdisadvantage of the p-phenylenediamine developers is that they arehighly allergenic, that is, they are poisonous to the human skin and aretherefore somewhat dangerous to use.

The allergenic properties of the p-phenylenediamine developers may beovercome by substituting a sulfonamide group or an amino sulfonyl groupin the alkyl group on the nitrogen atom of p-phenylenediamine asdescribed in Weissberger U. S. Patent 2,193,015, granted March 12, 1940.The substituted p-phenylenediamine developing agents are. however,sometimes too low in developing strength (reduction potential) so thatit is difficult to obtain, with them, dye images of sufiiciently highdensity and contrast.

It is therefore an object of the present invention to provide a newclass of photographic developing agents of the p-phenylenediamine type.30

A further object is to provide developing agents of thepphenylenediamine type which produce dye images having the desiredcharacteristics.

These objects are accomplished by the present invention by the use asdeveloping agents of compounds having the following general formula:

NHz

where R is a lower alkyl group such as methyl, ethyl, or propyl, R is alower alkyl group and X is hydrogen, a lower alkyl group or a loweralkoxy group.

By lower alkyl group, we mean a methyl, ethyl or propyl group. By loweralkoxy group we mean a methoxy, ethoxy or propoxy group.

Compounds of this class which may be used according to our invention areas follows:

1 11 C H NH C O CH:

NHz 4-amino-N-ethyl-N- (B-acetamidoethyl) -ani1ine z 0211, O H4NHCOCH3NH: 4-amlno-N-etl1yl-N- B-acetamidoethyl) -m-toluldine 3 C H5 C2H4NHO OCH; N

NHL

4-amino-N-ethyl-N- (B-acetamidoethyl -m-phenetidine The preparation ofour developers may be summarized by the following reaction scheme whichindicates the general method used in preparing compound 1. I

omomNnooom cmcnmnooon:

N 0 NH? The specific compounds illustrated above were prepared asfollows:

Compound 1, [4-amino-N-ethyl-N-( a-acetamidoethyD-aniline], was preparedfrom N-ethylaniline by the following series of reactions:

((1) N (o-aminoethyl) -N-ethyZaniZine.--A mixture of N-ethylaniline (2moles) and (fi-bromoethylamino hydrobromide (1 mole) was placed in aflask in an oil bath and the temperature of the oil bath was raised to145-150 C. during 45 minutes. The reaction mixture was stirred at thistemperature for 2 hours, cooled, diluted with water, and made alkalinewith 40% sodium hydroxide solution. The amine was extracted with ether,the ether solution was washed with water and the ether was evaporated.The residue was distilled under reduced pressure. The fraction thatboiled at 120-122 at 6 mm. was collected.

(7)) 4 amino N ethyl N (/8 acetamidoethyl) aniline.N (BaminoethyD-N-ethylaniline (1 mole) was added to 105 ml. of aceticanhydride with stirring and cooling so that the temperature did not riseabove 80. The solution was then heated at 100 for 30 minutes and dilutedwith 500 ml. of water. The mixture was acidified with 250 ml. ofconcentrated hydrochloric acid and stirred until solution took place.After cooling to the amine was nitrosated by the addition of a solutionof 70 g. of sodium nitrite in 150 m1. of water durin a period of 30minutes. The solution was stirred at 05 for minutes then furtheracidified by the addition of 200 ml. of concentrated hydrochloric acid.This solution was maintained at10i5 and 135 g. of zinc dust was added insmall portions during the course of 1 hour. The colorless solution wasfiltered to remove the excess zinc and made alkaline with 1 l. ofammonium hydroxide. The diamine was extracted with chloroform. Thechloroform solution was washed with water and dried over anhydroussodium sulfate. The chloroform was distilled at atmospheric pressure andthe diamine was distilled under reduced pressure. The portion thatboiled at 204-206 at 2 mm. was collected.

Compound 2, [4 amino N ethyl N (flacetamidoethyl) -m-toluidine], andCompound 3, [4 amino N ethyl N (13 acetamidoethyl) m-phenetidine], wereprepared from N-ethyl-mtoluidine and N-ethyl-m-phenetidine,respectively, by the same procedure used to prepare Compound 1 fromN-ethylaniline.

When used for the formation of colored photographic images, thedevelopers of our invention may be used in conjunction with anywell-known coupler compounds such as those described in Fisher U. S.Patent 1,102,028, granted June 30, 1914, Mannes and Godowsky U. S.Patent 2,108,- 602, granted February 15, 1938, or Mannes, Godowsky andPeterson U.- S. Patent 2,115,394, granted April 26, 1938 and 2,126,337,granted August 9, 1938.

The following example illustrates a developing solution which may beused according to our invention.

(a) 4 amino N ethyl N 3 acetamidoethyl) aniline grams 1 Sodium sulfitedo 2 Sodium carbonate do 30 Potassium bromide do 2 Water to 1 liter. (b)Coupler (2,4 dichloro 1 naphthol) grams 2 Sodium hydroxide (10%solution) .00..

For use (b) is added to (a).

The developin agents described in the present application may be used toform photographic images by development of exposed silver halidecontained in the usual gelatin carrier or in carriers such as collodion,water-permeable cellulose ester or water-permeable synthetic resin. Ourdeveloping agents may be used with photographic films containing thecoupler in the emulsion layer as described in Mannes and Godowsky U. S.Patent 2,304,940, granted December 15, 1942, or Jelley and Vittum U. S.Patent 2,322,027, granted June 15, 1943. When used in this way, adeveloping solution similar in composition to part (a) in the aboveexample is suitable.

It will be understood that the examples of modifications included hereinare illustrative only.

We claim:

1. A silver halide developing solution for producing a coloredphotographic image comprising a developing agent having the generalformula:

R\ CHzClZlzNlICOR' where R is a lower alkyl group, R is a lower alkylgroup and X is selected from the class consisting of hydrogen, loweralkyl and lower alkoxy groups, and a compound which couples with theoxidation product of said developing agent to form a colored image uponphotographic development.

2. A silver halide developing solution for producing a. coloredphotographic image comprising a substantial amount of 4-amino-N-ethyl-N-(p-acetamidoethyl) aniline, and a compound which couples with theoxidation product of said developing agent upon development to form acolored image.

3. A silver halide developing solution for producing a coloredphotographic image comprising a substantial amount of 4-amino-N-ethyl-N-(B-acetamidoethyl) -1n-toluidine, and a compound which couples with theoxidation products of said developing agent upon development to form acolored image.

4. A silver halide developing solution for producing a coloredphotographic image comprising a substantial amount of4-amino-N-et'nyl-N- (fJ-acetamidoethyl)-m-phenetidine, and a compoundwhich couples with the oxidation products of said developing agent upondevelopment to form a colored image.

ARNOLD WEISSBERGER. DUDLEY B. GLASS. PAUL W. VITTUM.

REFERENCES CITED The following references are of record in the

1. A SILVER HALIDE DEVELOPING SOLUTION FOR PRODUCING A COLOREDPHOTOGRAPHIC IMAGE COMPRISING A DEVELOPING AGENT HAVING THE GENERALFORMULA: